EP0407224A1 - Thermoplastische Harz-Zusammmensetzung - Google Patents
Thermoplastische Harz-Zusammmensetzung Download PDFInfo
- Publication number
- EP0407224A1 EP0407224A1 EP90307438A EP90307438A EP0407224A1 EP 0407224 A1 EP0407224 A1 EP 0407224A1 EP 90307438 A EP90307438 A EP 90307438A EP 90307438 A EP90307438 A EP 90307438A EP 0407224 A1 EP0407224 A1 EP 0407224A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyamide
- weight
- ethylene
- acid
- polyphenylene ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/905—Polyphenylene oxide
Definitions
- the present invention relates to novel polyphenylene ether polyamide blends having improved paint adhesion strength and excellent impact strength.
- polyphenylene ether polyamide blends containing at least one elastomeric material selected from ethylene- ⁇ -olefin-(diene) copolymers with a vinyl aromatic monomer and at least one unsaturated functional monomers selected from unsaturated nitrile monomers and alkyl(meth) acrylates grafted thereto as hereinafter defined have improved impact strength and paint adhesion strength as compared to polyphenylene ether polyamide blends containing at least one ethylene- ⁇ -olefin-(diene) copolymer without such combination of unsaturated monomers grafted thereto, or containing at least one ethylene- ⁇ -olefin-(diene) copolymers with excessive quantity of such unsaturated functional monomers and vinyl aromatic monomers grafted thereto.
- Blends of polyphenylene ether and polyamide have long been known.
- U.S.P. 3,379,792 taught improved processability of polyphenylene ethers by incorporating therein up to 25% by weight of polyamide.
- U.S.P. 4,315,086 teaches the use of liquid diene polymers, epoxy compounds and compounds having in the molecule both (a) a carbon-carbon double bond or a carbon-carbon triple bond and (b) a carboxylic acid, acid anhydride, acid amide, imide, carboxylic acid ester, amino or hydroxyl group as compatibilizers.
- EP 46040 teaches copolymers of vinyl aromatic compounds and either an alpha, beta-unsaturated dicarboxylic acid anhydride or an imide compound thereof as a compatibilizer.
- U.S.P. 4,659,763 teaches the use of quinone compounds
- U.S.P. 4,600,741 teaches the use of trimellitic anhydride acid chloride and the like
- U.S.P. 4,659,760 teaches the use of oxidized polyethylene wax
- WO 85/05372 teaches the use of polycarboxylic acids such as citric acid
- WO 87/07281 teaches the use of vinyltrimethoxy silane as compatibilizers.
- Japanese Kokai Patent TOKKAI SHO 63-33471 teaches the use of maleated ethylene-propylene-(diene) copolymers
- TOKKAI SHO 63-205350 teaches the use of acrylonitrile/styrene grafted ethylene-propylene(diene) copolymers
- TOKKAI SHO 63-312350 teaches the use of styrene grafted ethylene-propylene-(diene) copolymers.
- styrene grafted ethylene- ⁇ -olefin-(diene) copolymers improves the paint adhesion strength over ungrafted ethylene- ⁇ -olefin-(diene) copolymers to some extent but not to a satisfactory level.
- acrylonitrile/styrene grafted ethylene- ⁇ -olefin-(diene) copolymers were taught in TOKKAI SHO 63-205350. The impact strength of the blends, however, were poor due to the excessive content of styrene and acrylonitrile in the graftomers, although paint adhesion strength was excellent.
- thermoplastic composition of enhanced paint adhesion and excellent impact strength comprising polyphenylene ether, polyamide and ethylene- ⁇ -olefin-(diene) copolymer with a vinyl aromatic monomer and an unsaturated functional monomer grafted hereto, by optimizing the content of vinyl aromatic monomer and unsaturated monomer present in the graftomer as hereinafter disclosed.
- polyphenylene ether polyamide compositions having unexpectedly improved paint adhesion and high impact strength may be prepared by incorporating at least one elastomeric material selected from ethylene- ⁇ -olefin-(diene) copolymers with at least one vinyl aromatic monomer and at least one unsaturated functional monomer selected from unsaturated nitrile monomers and alkyl(meth) acrylates grafted thereto.
- compositions of the present invention are prepared from,
- composition of the present invention will generally be prepared from 5 to 95, preferably 30 to 70% by weight polyphenylene ether (A), and from about 95 to 5, preferably 70 to 30% by weight polyamide (B), 5 to 50, preferably 5 to 30 parts by weight of at least one of the elastomeric materials as herein defined (C), based on 100 parts by weight of the total of the polyphenylene ether and polyamide, and from about 0.01 to 30, preferably from about 0.1 to about 5 parts by weight of at least one compatibilizer (D), based on 100 parts by weight of the total of the polyphenylene ether and polyamide.
- A polyphenylene ether
- B polyamide
- C elastomeric materials as herein defined
- the polyphenylene ether component (A) used in the present invention is homopolymer or copolymer composed of the following repeating unit (I) or (I) and (II): wherein R1, R2, R3, R4, R5 and R6 which may be identical or different each represents a monovalent residue such as an alkyl group of 1 - 4 carbon atoms excluding tert-butyl group, an aryl group, a halogen atom or a hydrogen atom, and R3 and R5 cannot be simultaneously hydrogen atom.
- the polyphenylene ether may be a mixture of said homopolymer and said copolymer, or a graft copolymer of said polymer with styrene.
- the homopolymer of polyphenylene ether includes poly(2,6-dimethyl-1,4-phenylene)ether, poly(2-methyl-6-ethyl-1,4-phenylene)ether, poly(2,6-diethyl-1,4-phenylene)ether, poly(2-ethyl-6-n-propyl-1,4-phenylene)ether, poly(2,6 di-n-propyl-1,4-phenylene)ether, poly(2-methyl-6-n-butyl-1,4-phenylene)ether, poly(2-ethyl-6-isopropyl-1,4-phenylene)ether, poly(2-methyl-6-chloro-1,4-phenylene)ether, poly(2-methyl-6-hydroxyethyl-1,4-phenylene)ether and poly(2-methyl-6-chloroethyl-1,4-phenylene)ether.
- the copolymer of polyphenylene ether includes polyphenylene ether copolymers mainly composed of polyphenylene ether structure which is obtained by copolymerization with o-cresol or an alkyl-substituted phenol such as 2,3,6-trimethylphenol which is represented by the formula (III): wherein R3, R4, R5 and R6 each represents a monovalent residue such as an alkyl group of 1 - 4 carbon atoms excluding tert-butyl group, an aryl group, a halogen atom or a hydrogen atom, and R3 and R5 cannot be simultaneously hydrogen atom.
- the polyamide component (B) used in the present invention is well known in the art and may be selected from any of aliphatic polyamides or thermoplastic acromatic copolyamides or a combination thereof.
- the aliphatic polyamides have a molecular weight of 10,000 or more and can be produced by bonding of equimolar of a saturated aliphatic dicarboxylic acid of 4 - 12 carbon atoms and an aliphatic diamine of 2 - 12 carbon atoms.
- the diamines may be excessively used so as to provide more amine terminal groups than carboxyl terminal groups in the polyamide, or alternatively, a dibasic acid may be excessively used so as to provide more acid groups.
- these polyamides can be conveniently produced from acid production derivatives and amine production derivatives such as esters, acid chlorides and amine salts, of the above mentioned acids and amines.
- aliphatic dicarboxylic acid used for the production of the polyamides include adipic acid, pimelic acid, azelaic acid, suberic acid, sebacic acid and dodecanedioic acid.
- aliphatic diamines include hexamethylenediamine and octamethylenediamine, and the like.
- aliphatic polyamides may also be produced by self-condcnsation of lactam.
- polystyrene resin examples include polyhexamethylene adipamide (nylon 66), polyhexamethylene azelamide (nylon 69), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecanamide (nylon 612), poly-bis-(p-aminocyclohexyl)methane dodecanoamide, polytetramethylene adipamide (nylon 46) and polyamides produced by ring cleavage of lactam such as polycaprolactam (nylon 6) and polylauryl lactam.
- polyamides produced by polymerization of at least two amines or acids selected from those used for the production of the above-mentioned polymers for examples polymers produced from adipic acid, sebacic acid and hexametheylenediamine.
- the aliphatic polyamides further include blends of above-mentioned polyamides such as a blend of nylon 6 and nylon 66 including copolymers such as nylon 66/6.
- the aliphatic polyamides used in the present invention are polyhexamethylene adipamide (nylon 66), polycaprolactam (nylon 6) and a blend of polyhexamthylene adipamide (nylon 66) with polycaprolactam (nylon 6).
- the thermoplastic aromatic copolyamide is a copolyamide containing an aromatic component therein, for example, polyhexamethylene isophthalamide (nylon 6I).
- the copolyamide containing an aromatic component therein means a melt-polymerizable polyamide containing as a main component an aromatic amino acid and/or aromatic dicarboxylic acid such as para-aminomethylbenzoic acid, para-aminoethylbenzoic acid, terephthalic acid and isophthalic acid.
- Diamines which may constitute another component of the polyamide include hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-/2,4,4-trimethylhexamethylenediamine, m-xylylenediamine, p-xylylenediamine, bis(p-aminocyclohexyl)methane, bis(p-aminocyclohexyl)propane, bis(3-methyl-4-aminocyclohexyl) methane, 1,3-bis(aminomethyl)cyclohexane and 1,4-bis (aminomethyl)cyclohexane.
- An isocyanate may also be used in place of the diamine.
- any other comonomers may be used, if necessary.
- the comonomers are 4,4′-diphenylmethane diisocyanate and tolylene diisocyanate.
- Other exmaples thereof are a unit of lactam, a unit of ⁇ -amino acid of 4 - 12 carbon atoms, a compound derived from an aliphatic dicarboxylic acid of 4 - 12 carbon atoms and an aliphatic diamines of 2 - 12 carbon atoms, for example, lactams and amino acids such as ⁇ -caprolactam, nonalolactam, 11-aminoundecanoic acid and 12-aminododecanoic acid, and equimolar salts of the above-mentioned various diamines and adipic acid, azelaic acid or sebacic acid.
- thermoplastic aromatic copolyamides comprising these components are copolymer polyamide of p-aminomethylbenzoic acid and e-caprolactam (nylon AMBA/6), polyamides mainly composed of 2,2,4-/2,4,4-trimethylhexamethylenediamine ⁇ terephthalate (nylon TMDT and nylon TMDT/6I), polyamides mainly composed of hexamethylenediamine isophthalate and/or hexamethylene diamine ⁇ terephthalate and containing, as a comonomer, bis(p-aminocyclohexyl)methane ⁇ terephthalate, and/or bis(3-methyl-4-aminocyclohexyl)methane ⁇ isophthalate and/or bis(3-methyl-4-aminocyclohexyl)propane ⁇ isophthalate and/or bis(p-aminocyclohexyl)propane ⁇ terephthalate (nylon 6I
- the aromatic nuclear-hydrogenated copolyamide of component (B) is an alicyclic copolyamide obtained by using cyclohexane-1,4-dicarboxylic acid or cyclohexane-1,3-dicarboxylic acid obtained by nulear-hydrogenation of terephthalic acid or isophthalic acid in place of terephthalic acid or isophthalic acid which is an acid component of the above-mentioned aromatic copolyamides.
- nuclear-hydrogenation product of diamines or diisocyanates such as 4,4′-diphenylmethane diisocyanate or tolylene diisocyanate, may also be used as a monomer.
- the ethylene ⁇ -olefin (diene) copolymers useful for the practice of the present invention are well known in the art.
- the illustrative examples of the ethylene ⁇ -olefin (diene) copolymers include ethylene propylene copolymer often called EPR, ethylene propylene 1,4-hexadiene copolymer, ethylene propylene dicyclopentadiene copolymer, ethylene propylene ethylidene norbornene copolymer collectively often called EPDM, ethylene butene-1 copolymer, ethylene butene-1 ethylidene norbornene copolymer and the like.
- unsaturated nitrile monomers used herein means a compound having in its molecular structure at least one ethylenic carbon-carbon double bond or carbon-carbon triple bond and -CN radical.
- the preferred unsaturated nitrile monomers are acrylonitrile and methacrylonitrile.
- the most preferred unsaturated nitrile monomer is acrylonitrile.
- Alkyl(meth)acrylates useful for the practic of the present invention are well known in the art.
- the illustrative example of alkyl(meth)acrylates include methylmethacrylate, ethylmethacrylate, butylmethacrylate, glycidylmethacrylate, 2-ethylhexylmethacrylate, methylacrylate, ethylacrylate, butylacrylate and the like.
- the elastomeric material components (C) used for the practice of the present invention may be prepared by grafting at least one vinyl aromatic monomer and at least one of unsaturated nitrile monomers and/or alkylmethacrylates to at least one of ethylene- ⁇ -olefin (diene)-copolymers.
- Method for grafting of such monomers to the ethylene- ⁇ -olefin-(diene) copolymers is not critical in the practice of the present invention and any known method in the art may be employed. Melt mixing of the ethylene- ⁇ -olefin-(diene) copolymers and the grafting monomers with a suitable amount of a free radical initiator may be employed. Grafting of the said monomers under an aqueous suspension of ethylene ⁇ -olefin (diene) copolymers with a suitable amount of a free radical initiator and a dispersing agent may also be employed.
- the impact strength of the polyphenylene ether polyamide blends decreses.
- Graft Rubber ethylene- ⁇ -olefin-(diene) copolymer
- Graft Rubber will be from about 5 to 50, preferably 5 to 30 parts by weight per 100 parts by weight of the polyphenylene ether polyamide blends.
- Graft rubbers may further be functionalized with an unsaturated functional monomer including, but not limited to, maleic anhydride, fumaric acid, glycidylmethacrylate, acrylamide and the like.
- copolymers of unsaturated nitrile monomers such as acrylonitrile styrene copolymer often called SAN and/or alkyl(meth)acrylate polymers such as polymethylmethacrylate and methylmethacrylate butylacrylate copolymer to further enhance the paint adhesion strength if the need may be.
- unsaturated nitrile monomers such as acrylonitrile styrene copolymer often called SAN and/or alkyl(meth)acrylate polymers such as polymethylmethacrylate and methylmethacrylate butylacrylate copolymer to further enhance the paint adhesion strength if the need may be.
- Liquid diene polymers suitable for use herein include homopolymers of a conjugated diene and copolymers of a conjugated diene with at least one monomer selected from the group consisting of other conjugated dienes, vinyl monomer, e.g., ethylene, propylene, butene-1, isobutylene, hexene-1, octene-1 and dodecene-1, and mixtures thereof, having a number average molecular weight of from 150 to 10,000, preferably 150 to 5,000.
- vinyl monomer e.g., ethylene, propylene, butene-1, isobutylene, hexene-1, octene-1 and dodecene-1, and mixtures thereof, having a number average molecular weight of from 150 to 10,000, preferably 150 to 5,000.
- These homopolymers and copolymers include, among others, polybutadiene, polyisoprene, poly(1,3-pentadiene), poly(butadiene-isoprene), poly(styrene-butadiene), polychloroprene, poly(butadiene-alpha methyl styrene), poly(butadiene-styrene-isoprene), poly(butylene-butadiene) and the like.
- Epoxy compounds suitable for use in the practice of the present invention there are given (1) epoxy resins produced by condensing polyhydric phenols (e.g. bisphenol-A, tetrabromobisphenol-A, resorcinol and hydroquinone) and epichlorohydrin; (2) epoxy resins produced by condensing polyhydric alcohols (e.g.
- glycidyletherified products of monohydric compounds including phenyl glycidylether, allyl glycidylether, butyl glycidylether and cresyl
- the unsaturated functional compounds are those having in the molecule both (a) an ethylenic carbon-carbon double bond or a carbon-carbon triple bond and (b) at least one carboxylic acid, acid anhydride, acid halide, anhydride, acid halide anhydride, acid amide, acid ester, imide, amino, or hydroxy group.
- unsaturated polyfunctional compounds are maleic acid; maleic anhydride; fumaric acid; citraconic acid; itaconic acid; maleimide; maleic hydrazide; reaction products resulting from a diamine and maleic anhydride, maleic acid, fumaric acid, etc.; dichloromaleic anhydride; maleic acidamide; unsaturated monocarboxylic acid (such as acrylic acid, butenoic acid, methacrylic acid, ⁇ -ethylacrylic acid, pentenoic acid, decenoic acids, undecenoic acids, dodecenoic acids, linoleic acids); esters, acid amides or anhydrides of the foregoing unsaturated carboxylic acids including glycidyl(meth) acrylate; unsaturated alcohols (such as allyl alcohol, crotyl alcohol, methyl vinyl carbinol, 4-pentene-1-ol, 1,4-hexadiene-3-ol, 3-butene-1
- the aliphatic polycarboxylic acid compounds or the derivatives thereof suitable are represented by the formula: (R I O) m R(COOR II ) n (CONR III R IV ) s wherein R is a linear or branched chain, saturated aliphatic hydrocarbon of from 2 to 20, preferably 2 to 10 carbon atoms; R I is selected from the group consisting of hydrogen or an alkyl, aryl, acyl or carbonyl dioxy group of 1 to 10, preferably 1 to 6, most preferably 1 to 4 carbon atoms, especially preferred is hydrogen; each R II is independently selected from the group consisting of hydrogen or an alkyl or aryl group of from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms; each R III and R IV is independently selected from the group consisting essentially of hydrogen or an alkyl or aryl group of from 1 to 10, preferably from 1 to 6, most preferably 1 to 4 carbon atoms; m is equal to 1 and (n + s) is greater than or equal to
- Suitable polycarboxylic acids are citric acid, malic acid, and agaricic acid.
- the polyfunctional acid halide compounds suitable for use herein are characterized as having both (a) at least one acid halide group, preferably acid chloride group and (b) at least one carboxylic acid, carboxylic acid anhydride, acid ester or acid amide group, preferably a carboxylic acid or carboxylic acid anhydride group.
- compatibilizers within this group are trimellitic anhydride acid chloride, chloroformyl succinic anhydride, and the like.
- the total amount of one or more of the compatibilizing agent used herein will be dependent on the specific compatibilizing agent selected. It is desirable to use at least necessary enough amount in enhancing the compatibility of the polyphenylene ether polyamide blend. Generally the amount of compatibilizing agent will be from about 0.01 to 30, preferably from about 0.1 to about 5 parts by weight per 100 parts by weight of the polyphenylene ether polyamide blend.
- Blending method of the components (A), (B), (C) and (D) is not critical.
- Known melt kneading methods can be employed as the blending method. Extruders, kneaders, rolls and the like may be used. Preferably extruders can be used as melt kneading apparatuses. There is no special limitation in sequence of addition of the components upon melt kneading.
- polyphenylene ether polyamide blends may further comprise inorganic fillers such as talc, aluminosilicate, mica, carbon black, glass fiber and the like, pigments, heat stabilizers, ultraviolet degradation inhibitors, antioxidants, flame retardants, plasticizers and the like.
- inorganic fillers such as talc, aluminosilicate, mica, carbon black, glass fiber and the like, pigments, heat stabilizers, ultraviolet degradation inhibitors, antioxidants, flame retardants, plasticizers and the like.
- thermoplastic resin composition of the present invention can be used suitably for automobile parts and electrical and electronic parts.
- exterior trim parts such as bumper, fender, apron, hood panel, fascia, rocker panel, rocker panel reinforce, floor panel, rear quarter panel, door panel, door support, roof top, and trunk lid
- interior trim parts such as instrument panel, console box, glove box, shift knob, pillar garnish, door trim, handle, arm rest, wind louver, carpet, seat belt, and seat
- interior parts of engine room such as distributor cap, air cleaner, radiator tank, battery case, radiator shroud, washer tank, cooling fan, and heater case, mirror body, wheel cover, trunk trim, trunk mat and the like.
- a styrene/acrylonitrile grafted EPDM was prepared by suspension graft copolymerization.
- a styrene/acrylonitrile grafted EPDM obtained contained 24.7 wt% of styrene component, 1.5 wt% of acrylonitrile component.
- the content of acrylonitrile monomer in the total of polymerized styrene and acrylonitrile was 5.1 wt%.
- Graft Rubber B was prepared in the same manner as in the preparation of Graft Rubber A except that EPDM was substituted with EPR (Sumitomo Chemical Co., Ltd.'s Esprene E-100).
- Graft Rubber C was prepared in the same manner as in the preparation of Graft Rubber A except that acrylonitrile was substituted with methylmethacrylate.
- Graft Rubbers D through J were prepared in the same manner as in the preparation of Graft Rubber A except that the quantity of styrene and acrylonitrile charged were changed as shown in each column of Table-I, and that the quantity of benzoyl peroxide was adjusted in proportion to the total quantity of styrene and the functional monomer.
- the extruder had L/D ratio of 32 and was equipped with a first feed opening at the position of L/D ratio of 1 and with a second feed opening at the position of L/D ratio of 16. (L: the length of the screw, D: the diameter of the screw).
- the cylinder temperature was set at about 260°C and screw speed was set at 360 rpm.
- the formulation of the individual blend was shown in Table-II.
- the paint adhesion strength and Izod Impact Strength measured of each blend were also shown in Table-II.
- compatibilizer and free radical initiator were shown in parts by weight per 100 parts of the total of the polymeric materials and each of the polymeric materials was shown in weight % of the total of the polymeric materials.
- the feed rate of the first feed and the second feed were controlled by the automatic weight feed control system so as to maintain the formulation of the individual blend as specified in Table-II.
- the polyphenylene ether employed in the examples was either polyphenylene ether having a reduced viscosity of 0.52 dl/g (hereinafter denoted as PPE-A) or polyphenylene ether having a reduced viscosity of 0.42 dl/g (hereinafter denoted as PPE-B) measured at 25 °C in a chloroform solution of 0.5 g/dl concentration manufactured by Nippon Polyether Kabushiki Kaisha.
- Polymethylmethacrylate if employed in any of the examples was Sumitomo Chemical Co., Ltd.'s Sumipex® LG.
- Acrylonitrile styrene copolymer if employed in any of the examples was Sumitomo Naugatuck Co., Ltd.'s Clearpet ® 1,000.
- the free radical initiator if employed, was dicumyl peroxide, Sanperox® DCP made by Sanken Kako Kabushiki Kaisha.
- the free radical initiator if employed, was always preblended with polyphenylene ether and fed from the first feed opening. Polyphenylene ether was always fed from the first feed opening and polyamides were always fed from the second opening.
- the paint adhesion test was performed in the following manner;
- the cured paint layer was cross cut by a sharp edged knife so as to make one hundred of 2 mm by 2 mm square pieces of the layer. Then a sheet of adhesive tape was applied on to the cross cut surface and the tape was peeled off.
- the paint adhesion strength was measured by counting the number of about 2 mm by 2 mm square pieces remained unpeeled off, out of the 100 cross cut pieces.
- the paint used in the examples was "Origiplate Z-NY metallic silver” manufactured by Origin Denki Kabushiki Kaisha.
- the impact strength of the blends were measured in terms of Izod Impact Strength according to the method specified in ASTM D-256.
- the premix prepared for the first feed opening will be referred to as the first feed premix hereinafter.
- 20 Kg of the nylon 6 and 5 kg of the nylon 66 were premixed as prescribed in the Feed-2 column of Example-1 of Table-II using the same tumbler mixer for 30 minutes prior to the feeding to the second feed opening of the TEX-44 twin screw extruder.
- the premix prepared for the second feed opening will be referred to as the second feed premix hereinafter.
- the cylinder temperature of the extruder was set at about 260 °C and the screw speed, at about 360 rpm.
- the first feed premix was fed to the first feed opening at a rate of 20.2 kg/hr and the second feed premix was fed to the second feed opening at a rate of 20 kg/hr so as to maintain the formulation of the ingredients shown in Example-1.
- the paint adhesion strength was tested with 5 of the plates according to the test method described before. The abarage of the paint adhesion strength measured of the five plates was shown in the Table-II. Izod Impact Strength measured was also shown in Table-II.
- Example-3 of Table-II The experiment was conducted in the same manner as in Example-1 except that Graft Rubber A was substituted with Graft Rubber C and the blend of polyamide 6 and polyamide 66 was substituted with polyamide 6, as shown in Example-3 of Table-II.
- Example-4 The experiment was conducted in the same manner as in Example-2 except that 1 kg out of 20 kg of polyphenylene ether was substituted with PMMA, as shown in Example-4 of Table-II.
- Example-4 The experiment was conducted in the same manner as in Example-4 except that PMMA was substituted with the same amount of acrylonitrile styrene copolymer (SAN) as shown in Example-5 of Table-II.
- SAN acrylonitrile styrene copolymer
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Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US376739 | 1989-07-07 | ||
| US07/376,739 US5084511A (en) | 1989-07-07 | 1989-07-07 | Thermoplastic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0407224A1 true EP0407224A1 (de) | 1991-01-09 |
| EP0407224B1 EP0407224B1 (de) | 1994-06-01 |
Family
ID=23486267
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90307438A Expired - Lifetime EP0407224B1 (de) | 1989-07-07 | 1990-07-06 | Thermoplastische Harz-Zusammmensetzung |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5084511A (de) |
| EP (1) | EP0407224B1 (de) |
| JP (1) | JP3242645B2 (de) |
| CA (1) | CA2020440A1 (de) |
| DE (1) | DE69009316T2 (de) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0381390A3 (de) * | 1989-01-31 | 1992-01-22 | Sumitomo Chemical Company, Limited | Thermoplastische Harzzusammensetzung |
| EP0602945A1 (de) * | 1992-12-16 | 1994-06-22 | Sumitomo Chemical Company, Limited | Zusammensetzungen aus Polyphenylenether und Polyamid |
| US5424360A (en) * | 1992-12-16 | 1995-06-13 | Sumitomo Chemical Company, Limited | Thermoplastic resin composition |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5231146A (en) * | 1990-09-20 | 1993-07-27 | General Electric Company | Polyphenylene ether-polyetheramide blends |
| US5225270A (en) * | 1991-12-24 | 1993-07-06 | Allied-Signal Inc. | Compatibilized polyphenylene ether/polyamide monofilament and felt made therefrom |
| CA2082726A1 (en) * | 1991-12-31 | 1993-07-01 | John B. Yates, Iii | Polyphenylene ether alloys |
| US5310776A (en) * | 1992-05-13 | 1994-05-10 | Mitsubishi Petrochemical Co., Ltd. | Process for preparing thermoplastic resin composition |
| US5554677A (en) * | 1992-06-09 | 1996-09-10 | Sumitomo Chemical Company, Limited | Blow-molded article made from thermoplastic resin composition |
| US5470902A (en) * | 1992-10-21 | 1995-11-28 | Sumitomo Wiring Systems, Ltd. | Resin composition for automobile relay box and automobile relay box comprising the same |
| EP0609792A1 (de) * | 1993-02-03 | 1994-08-10 | Basf Corporation | Modifizierte Fasern aus Nylon |
| EP0610890A3 (de) * | 1993-02-09 | 1995-09-13 | Mitsubishi Gas Chemical Co | Thermoplastische Harzzusammensetzungen aus Polyphenylenethern. |
| US5336732A (en) * | 1993-02-12 | 1994-08-09 | Alliedsignal Inc. | Process for forming polyamide/poly(phenylene ether) blends |
| US20050228109A1 (en) * | 2004-04-07 | 2005-10-13 | Tapan Chandra | Thermoplastic compositions with improved paint adhesion |
| US9289795B2 (en) | 2008-07-01 | 2016-03-22 | Precision Coating Innovations, Llc | Pressurization coating systems, methods, and apparatuses |
| US20100015456A1 (en) * | 2008-07-16 | 2010-01-21 | Eastman Chemical Company | Thermoplastic formulations for enhanced paintability toughness and melt process ability |
| US8734909B2 (en) * | 2010-03-10 | 2014-05-27 | Eastman Chemical Company | Methods and apparatus for coating substrates |
| JP5695845B2 (ja) * | 2010-06-15 | 2015-04-08 | ユーエムジー・エービーエス株式会社 | 成形用熱可塑性樹脂組成物およびその製造方法、成形品およびその製造方法 |
| US9616457B2 (en) | 2012-04-30 | 2017-04-11 | Innovative Coatings, Inc. | Pressurization coating systems, methods, and apparatuses |
| US8865261B2 (en) | 2012-12-06 | 2014-10-21 | Eastman Chemical Company | Extrusion coating of elongated substrates |
| US9920526B2 (en) | 2013-10-18 | 2018-03-20 | Eastman Chemical Company | Coated structural members having improved resistance to cracking |
| US9744707B2 (en) | 2013-10-18 | 2017-08-29 | Eastman Chemical Company | Extrusion-coated structural members having extruded profile members |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0046040A1 (de) * | 1980-08-13 | 1982-02-17 | Asahi Kasei Kogyo Kabushiki Kaisha | Thermoplastische Harzzusammensetzung mit hoher Temperatur- und Ölbeständigkeit und daraus gebildete Gegenstände |
| EP0024120B1 (de) * | 1979-08-08 | 1983-04-06 | Sumitomo Chemical Company, Limited | Harzzusammensetzungen, enthaltend Polyphenyleneoxyd, Polyamid und eine Verbindung zur Verbesserung der Schlagfestigkeit |
| EP0270246A2 (de) * | 1986-10-31 | 1988-06-08 | Sumitomo Chemical Company, Limited | Thermoplastische Harzzusammensetzung |
| EP0299619A2 (de) * | 1987-06-12 | 1989-01-18 | Sumitomo Chemical Company, Limited | Thermoplastische Harzzusammentsetzung |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3379792A (en) * | 1965-08-12 | 1968-04-23 | Gen Electric | Polymer blend of a polyphenylene oxide and a polyamide |
| US4315086A (en) * | 1979-08-08 | 1982-02-09 | Sumitomo Chemical Company, Limited | Resin compositions |
| JPS5959724A (ja) * | 1982-09-29 | 1984-04-05 | Unitika Ltd | 熱可塑性樹脂変性体の製造方法 |
| JPS5986653A (ja) * | 1982-11-08 | 1984-05-18 | Unitika Ltd | 樹脂組成物 |
| NL8401545A (nl) * | 1984-05-14 | 1985-12-02 | Gen Electric | Polymeermengsel dat een polyfenyleenether en een polyamide bevat. |
| JPH0668071B2 (ja) * | 1984-05-21 | 1994-08-31 | ゼネラル エレクトリツク カンパニイ | 変性されたポリフェニレンエーテル―ポリアミド組成物の製造法 |
| US4600741A (en) * | 1984-09-27 | 1986-07-15 | General Electric Company | Polyphenylene ether-polyamide blends |
| NL8502116A (nl) * | 1985-07-24 | 1987-02-16 | Gen Electric | Werkwijze voor het bereiden van een polymeermengsel, dat een polyfenyleen ether en een polyamide bevat. |
| US4654405A (en) * | 1985-12-05 | 1987-03-31 | Borg-Warner Chemicals, Inc. | Carboxylated phenylene ether resins |
| US4659763A (en) * | 1986-01-06 | 1987-04-21 | General Electric Company | Modified polyphenylene ether-polyamide compositions |
| NL8600166A (nl) * | 1986-01-27 | 1987-08-17 | Gen Electric | Polymeermengsel, dat een polyamide, een polyfenyleenether en een middel voor het verbeteren van de slagsterkte bevat. |
| JPH0794601B2 (ja) * | 1986-04-09 | 1995-10-11 | 旭化成工業株式会社 | 難燃性樹脂組成物 |
| US4732937A (en) * | 1986-05-27 | 1988-03-22 | General Electric Company | Epoxide-functionalized polyphenylene ethers and method of preparation |
| WO1987007281A1 (en) * | 1986-05-27 | 1987-12-03 | General Electric Company | Functionalized polyphenylene ethers, method of preparation, and polyphenylene ether-polyamide compositions prepared therefrom |
| JPS63113071A (ja) * | 1986-10-31 | 1988-05-18 | Mitsubishi Petrochem Co Ltd | 樹脂組成物 |
| JP2512450B2 (ja) * | 1986-10-23 | 1996-07-03 | 三菱化学株式会社 | 樹脂組成物 |
| EP0302897A1 (de) * | 1987-02-12 | 1989-02-15 | General Electric Company | Polyphenylenäther-polyamidmischungen |
| JPS63205350A (ja) * | 1987-02-20 | 1988-08-24 | Japan Synthetic Rubber Co Ltd | 熱可塑性樹脂組成物 |
| JPH01139642A (ja) * | 1987-11-26 | 1989-06-01 | Mitsubishi Kasei Corp | 樹脂組成物 |
-
1989
- 1989-07-07 US US07/376,739 patent/US5084511A/en not_active Expired - Fee Related
-
1990
- 1990-07-03 JP JP17447290A patent/JP3242645B2/ja not_active Expired - Fee Related
- 1990-07-04 CA CA002020440A patent/CA2020440A1/en not_active Abandoned
- 1990-07-06 DE DE69009316T patent/DE69009316T2/de not_active Expired - Fee Related
- 1990-07-06 EP EP90307438A patent/EP0407224B1/de not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0024120B1 (de) * | 1979-08-08 | 1983-04-06 | Sumitomo Chemical Company, Limited | Harzzusammensetzungen, enthaltend Polyphenyleneoxyd, Polyamid und eine Verbindung zur Verbesserung der Schlagfestigkeit |
| EP0046040A1 (de) * | 1980-08-13 | 1982-02-17 | Asahi Kasei Kogyo Kabushiki Kaisha | Thermoplastische Harzzusammensetzung mit hoher Temperatur- und Ölbeständigkeit und daraus gebildete Gegenstände |
| EP0270246A2 (de) * | 1986-10-31 | 1988-06-08 | Sumitomo Chemical Company, Limited | Thermoplastische Harzzusammensetzung |
| EP0299619A2 (de) * | 1987-06-12 | 1989-01-18 | Sumitomo Chemical Company, Limited | Thermoplastische Harzzusammentsetzung |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0381390A3 (de) * | 1989-01-31 | 1992-01-22 | Sumitomo Chemical Company, Limited | Thermoplastische Harzzusammensetzung |
| US5559185A (en) * | 1989-01-31 | 1996-09-24 | Sumitomo Chemical Company, Limited | Thermoplastic resin composition |
| EP0602945A1 (de) * | 1992-12-16 | 1994-06-22 | Sumitomo Chemical Company, Limited | Zusammensetzungen aus Polyphenylenether und Polyamid |
| US5424360A (en) * | 1992-12-16 | 1995-06-13 | Sumitomo Chemical Company, Limited | Thermoplastic resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3242645B2 (ja) | 2001-12-25 |
| EP0407224B1 (de) | 1994-06-01 |
| DE69009316D1 (de) | 1994-07-07 |
| JPH03215553A (ja) | 1991-09-20 |
| CA2020440A1 (en) | 1991-01-08 |
| US5084511A (en) | 1992-01-28 |
| DE69009316T2 (de) | 1994-09-15 |
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